Fungicidal and plant growth-regulating azolylmethyl-cyclopropyl derivatives

ABSTRACT

Fungicidal and plant growth-regulating azolylmethylcyclopropyl derivatives of the formula ##STR1## in which R represents halogen, alkyl or optionally substituted phenyhl, or represents the groupings --Y--R 2 , 
     wherein 
     Y represents oxygen, sulphur, SO or SO 2  and 
     R 2  represents optionally substituted phenyl, 
     R 1  represents hydrogen, alkyl or acyl, 
     X represents nitrogen or a CH group, 
     Z represents halogen, alkyl with 1 to 4 carbon atoms, alkoxy with 1 to 4 carbon atoms, alkylthio with 1 to 4 carbon atoms, halogenoalkyl with 1 or 2 carbon atoms and 1 to 5 halogen atoms, halogenoalkoxy with 1 or 2 carbon atoms and 1 to 5 halogen atoms, halogenoalkylthio with 1 or 2 carbon atoms and 1 to 5 halogen atoms or phenyl which is optionally substituted by alkyl with 1 or 2 carbon atoms and/or halogen, or represents phenoxy which is optionally substituted by alkyl with 1 or 2 carbon atoms and/or halogen and 
     m represents the number 0, 1, 2 or 3, and addition products thereof with acids and metal salts. Intermediates therefor of the formulas ##STR2## are also new.

This is a division of application Ser. No. 206,403, filed June 14, 1988,now U.S. Pat. No. 4,913,727.

The present invention relates to new azolylmethylcyclopropylderivatives, several processes for their preparation and their use asfungicides and plant growth regulators.

It is already known that certain azolylmethylcyclopropyl-carbinolderivatives have fungicidal and plant growth-regulating properties(compare EP-OS (European Published Specification) No. 0,180,136). Thus,for example1-(4-chlorophenyl)-1-(1-chlorocyclopropyl)-2-(1,2,4-triazol-1-yl)-ethan-1-oland1-(4-fluorophenyl)(1-chloro-cyclopropyl)-2-(1,2,4-triazol-1-yl)-ethan-1-olcan be used for combating fungi and for regulating plant growth. Theactivity of these substances is good; however, in some cases they leavesomething to be desired when low amounts are applied.

It is furthermore known that certain hydroxyethyl-azolyl derivativessubstituted by cycloalkyl have fungicidal properties (compare EP-OS(European Published Specification) No. 0,015,756). However, the activityof these substances is also not always completely adequate.

New azolylmethyl-cyclopropyl derivatives of the formula ##STR3## inwhich

R represents halogen, alkyl or optionally substituted phenyl, orrepresents the grouping -Y-R²,

wherein

Y represents oxygen, sulphur, SO or SO₂ and

Y represents oxygen, sulphur, SO or SO₂ and

R² represents optionally substituted phenyl,

R¹ represents hydrogen, alkyl or acyl,

X represents nitrogen or a CH group,

Z represents halogen, alkyl with 1 to 4 carbon atoms, alkoxy with 1 to 4carbon atoms, alkylthio with 1 to 4 carbon atoms, halogenoalkyl with 1or 2 carbon atoms and 1 to 5 halogen atoms, halogenoalkoxy with 1 or 2carbon atoms and 1 to 5 halogen atoms, halogenoalkylthio with 1 or 2carbon atoms and 1 to 5 halogen atoms or phenyl which is optionallysubstituted by alkyl with 1 or 2 carbon atoms and/or halogen, orrepresents phenoxy which is optionally substituted by alkyl with 1 or 2carbon atoms and/or halogen and

m represents the number 0, 1, 2 or 3,

and acid addition salts and metal salt complexes thereof have now beenfound.

It has furthermore been found that azolylmethylcyclopropyl derivativesof the formula (I) and acid addition salts and metal salt complexesthereof are obtained by a process in which

(a) propanol derivatives of the formula ##STR4## in which

R, Z and m have the abovementioned meaning and

Hal represents chlorine, bromine or iodine,

are reacted with azoles of the formula ##STR5## in which

X has the abovementioned meaning,

in the presence of an acid-binding agent and in the presence of adiluent, or

(b) oxiranes of the formula ##STR6## in which

R, Z and m have the abovementioned meaning,

are reacted with azoles of the formula ##STR7## in which

X has the abovementioned meaning,

in the presence of an acid-binding agent and in the presence of adiluent, or

(c) azolylmethyl-ketones of the formula ##STR8## in which

R and X have the above-mentioned meaning,

are reacted with organometallic compounds of the formula ##STR9## inwhich

Z and m have the above-mentioned meaning and

X¹ represents chlorine, bromine or iodine,

in the presence of a diluent, or

(d) azolylmethyl-cyclopropyl-carbinol derivatives of the formula##STR10## in which

R, X, Z and m have the abovementioned meaning,

are reacted with strong bases in the presence of a diluent, and thealcoholates thereby formed, of the formula ##STR11## in which

R, X, Z and m have the abovementioned meaning and

R³ represents a cationic radical of a base,

are reacted with halogen compounds of the formula

    R.sup.4 -Hal'                                              (VII)

in which

R⁴ represents alkyl or acyl and

Hal' represents halogen,

in the presence of a diluent, and, if appropriate, an acid or a metalsalt is then added onto the compounds of the formula (I) thus obtained.

Finally, it has been found that the new azolylmethyl-cyclopropylderivatives of the formula (I) and acid addition salts and metal saltcomplexes thereof have powerful fungicidal and plant growth-regulatingproperties.

The substances according to the invention contain an asymmetricallysubstituted carbon atom. They can therefore be obtained in opticalisomer forms. The present invention relates both to the individualisomers and to mixtures thereof.

Surprisingly, the substances according to the invention have a betterfungicidal and plant growth-regulating activity than the already knowncompounds which are structurally the most similar and have the same typeof action.

Formula (I) provides a general definition of theazolylmethyl-cyclopropyl derivatives according to the invention.Preferably, in this formula,

R represents fluorine, chlorine, bromine or alkyl with 1 to 6 carbonatoms, or represents phenyl which is optionally substituted by halogen,halogenoalkyl with 1 or 2 carbon atoms and 1 to 5 halogen atoms, alkylwith 1 to 4 carbon atoms and/or alkoxy with 1 to 4 carbon atoms, orrepresents the grouping -Y-R²,

wherein

Y represents oxygen, sulphur, SO or SO₂ and

R² represents phenyl which is optionally substituted by halogen,halogenoalkyl with 1 or 2 carbon atoms and 1 to 5 halogen atoms, alkylwith 1 to 4 carbon atoms and/or alkoxy with 1 to 4 carbon atoms,

R¹ represents hydrogen, alkyl with 1 to 6 carbon atoms or alkylcarbonylwith 1 to 6 carbon atoms in the alkyl group,

X represents nitrogen or a CH group,

Z represents fluorine, chlorine, bromine, methyl, ethyl, isopropyl,tert.-butyl, methoxy, methylthio, trifluoromethyl, trifluoromethoxy,trifluoromethylthio or phenyl which is optionally substituted byfluorine, chlorine and/or methyl, or represents phenoxy which isoptionally substituted by fluorine, chlorine and/or methyl and

m represents the number 0, 1, 2 or 3.

If m represents the number 2 or 3, the radicals represented by Z can beidentical or different.

Particularly preferred compounds of the formula (I) are those in which

R represents fluorine, chlorine bromine, methyl, ethyl or phenyl whichis optionally substituted by one to three identical or differentsubstituents from the group comprising fluorine, chlorine, bromine,trifluoromethyl, methyl, ethyl, methoxy and/or ethoxy, or represents thegrouping -Y-R²,

wherein

Y represents oxygen, sulphur, SO or SO₂ and

R² represents phenyl which is optionally substituted by one to threeidentical or different substituents from the group comprising fluorine,chlorine, bromine, trifluoromethyl, methyl, ethyl, methoxy and/orethoxy,

R¹ represents hydrogen, methyl, ethyl, n-propyl, isopropyl, n-butyl,isobutyl, methylcarbonyl, ethylcarbonyl, n-propylcarbonyl,isopropylcarbonyl, n-butyl-carbonyl or isobutyl-carbonyl,

X represents nitrogen or a CH group,

Z represents fluorine, chlorine, bromine, methyl, ethyl, isopropyl,tert.-butyl, methoxy, methylthio, trifluoromethyl, trifluoromethoxy,trifluoromethylthio or phenyl which is optionally substituted byfluorine, chlorine and/or methyl, or represents phenoxy which isoptionally substituted by fluorine, chlorine and/or methyl and

m represents the number 0, 1, 2 or 3.

Addition products of acids and those azolylmethyl-cyclopropylderivatives of the formula (I) in which R, R¹, X, Z and m have themeanings which have already been mentioned as preferred for theseradicals and this index are also preferred compounds according to theinvention.

The acids which can be added on include, preferably, hydrogen halideacids, such as, for example, hydrochloric acid and hydrobromic acid, inparticular hydrochloric acid, and furthermore phosphoric acid, nitricacid, sulphuric acid, mono- and bifunctional carboxylic acids andhydroxycarboxylic acids, such as, for example, acetic acid, maleic acid,succinic acid, fumaric acid, tartaric acid, citric acid, salicylic acid,sorbic acid and lactic acid, and sulphonic acids, such as, for example,p-toluenesulphonic acid, 1,5-naphthalenedisulphonic acid orcamphorsulphonic acid.

Addition products of salts of metals of main groups II to IV and ofsub-groups I and II and IV to VIII of the periodic table of the elementsand those azolyl-methyl-cyclopropyl derivatives of the formula (I) inwhich R, R¹, X, Z and m have the meanings which have already beenmentioned as preferred for these radicals and this index are alsopreferred compounds according to the invention.

Salts of copper, zinc, manganese, magnesium, tin, iron and nickel areparticularly preferred here. Possible anions of these salts are thosewhich are derived from those acids which lead to physiologicallyacceptable addition products. Particularly preferred acids of this typeare, in this connection, the hydrogen halide acids, such as, forexample, hydrochloric acid and hydrobromic acid, and furthermorephosphoric acid, nitric acid and sulphuric acid.

The substances listed in the following table may be mentioned asexamples of azolylmethyl-cyclopropyl derivatives of the formula (I).

                  TABLE                                                           ______________________________________                                         ##STR12##                     (I)                                            Z.sub.m    R.sup.1    X        R                                              ______________________________________                                        4-Cl       H          N        Cl                                             2,4-Cl.sub.2                                                                             "          "        Cl                                             2,4-F.sub.2                                                                              "          "        Cl                                             4-CH.sub.3 "          "        Cl                                             4-CF.sub.3 "          "        Cl                                             4-OCF.sub.3                                                                              "          "        Cl                                             4-OCH.sub.3                                                                              "          "        Cl                                             4-SCH.sub.3                                                                              "          "        Cl                                             2,4,6-Cl.sub.3                                                                           "          "        Cl                                             4-Cl       "          "        F                                              4-Cl       "          CH       Cl                                             4-Cl       CH.sub.3   N        Cl                                             4-Cl       H          "                                                                                       ##STR13##                                     4-Cl       "          "                                                                                       ##STR14##                                     4-Cl       "          "                                                                                       ##STR15##                                     4-Cl       "          "                                                                                       ##STR16##                                     4-Cl       "          "                                                                                       ##STR17##                                      ##STR18## "          "        Cl                                              ##STR19## "          "        Cl                                             4-C.sub.4 H.sub.9 -t,                                                                    "          "        Cl                                             2-Cl, 4-CH.sub.3                                                                         "          "        Cl                                             --         "          "        Cl                                             4-Cl       COCH.sub.3 "        Cl                                             4-Cl       C.sub.2 H.sub.5                                                                          "        Cl                                             4-F        CH.sub.3   "        F                                              4-Cl       H          "        CH.sub.3                                       ______________________________________                                    

If 1-chloro-2-(1-chlorocyclopropyl)-3-(4-fluorophenyl)-propan-2-ol and1,2,4-triazole are used as starting substances, the course of process(a) according to the invention can be illustrated by the followingequation: ##STR20##

If 2-{(4-fluorophenyl)-methyl}-2-(1-chloro-cyclopropyl)-oxirane and1,2,4-triazole are used as starting substances, the course of process(b) according to the invention can be illustrated by the followingequation: ##STR21## If(1,2,4-triazol-1-yl-methyl)-(1-chloro-cycloprop-1-yl)-ketone and4-fluorobenzyl-magnesium bromide are used as starting substances, thecourse of the process (c) according to the invention can be illustratedby the following equation: ##STR22##

If1-(4-fluorophenyl)-2-(1-chlorocyclopropyl)-3-(1,2,4-triazol-1-yl)-propan-2-oland sodium hydride are used as starting substances and iodomethane isused as the reaction component, the course of process (d) according tothe invention can be illustrated by the following equation: ##STR23##

Formula (II) provides a general definition of the propanol derivativesrequired as starting substances in process (a) according to theinvention. In this formula, R, Z and m preferably have those meaningswhich have already been mentioned as preferred for these radicals andthis index in connection with the description of the substances of theformula (I) according to the invention. Hal preferably representschlorine or bromine.

The propanol derivatives of the formula (II) are as yet still unknown.They can be prepared by a process in which cyclopropyl ketones of theformula ##STR24## in which

R has the abovementioned meaning and

Hal" represents chlorine or bromine, are reacted with organometalliccompounds of the formula ##STR25## in which

X¹, Z and m have the abovementioned meaning,

in the presence of a diluent.

The cyclopropyl ketones of the formula (VIII) required as startingsubstances in the preparation of the propanol derivatives by the aboveprocess are known in some cases. They can be prepared by a process inwhich ketones of the formula ##STR26## in which

R has the abovementioned meaning, are reacted with chlorinating agentsor brominating agents in the presence of a diluent.

The ketones of the formula (IX) required as starting substances in thepreparation of cyclopropyl ketones of the formula (VIII) are known orcan be synthesized by processes which are known in principle (compareSynthesis 1977, 189).

Possible chlorinating agents and brominating agents in the above processfor the preparation of cyclopropyl ketones of the formula (VIII) are allthe chlorinating and brominating reagents which are customary for suchreactions. Sulphuryl chloride, sulphuryl bromide and bromine canpreferably be used.

Possible diluents in the preparation of cyclopropyl ketones of theformula (VIII) by the above process are all the inert organic solventswhich are customary for such reactions. Solvents which can preferably beused are halogenated aliphatic hydrocarbons, such as methylene chloride,chloroform and carbon tetrachloride

The temperatures can be varied within a certain range in the aboveprocess for the preparation of cyclopropyl ketones of the formula(VIII). The process is in general carried out at temperatures between-10° C. and +60° C., preferably between 0° C. and +40° C.

The above process for the preparation of cyclopropyl ketones of theformula (VIII) is in general carried out under normal pressure. However,it is also possible for the process to be carried out under increased orreduced pressure.

In carrying out the above process for the preparation of cyclopropylketones of the formula (VIII), in general a stoichiometric amount or aslight excess of chlorinating or brominating agent is employed per molof ketone of the formula (IX). Working up is by customary methods. Aprocedure is in general followed in which the reaction mixture is washedwith dilute aqueous sodium bicarbonate solution and with water insuccession and is then dried and concentrated.

The organometallic compounds of the formula (VI) required as reactioncomponents in the above process for the preparation of propanolderivatives of the formula (II) are known or can be synthesized bymethods which are known in principle. Thus, compounds of the formula(VII) are obtained by a process in which benzyl halides of the formula##STR27## in which

X¹, Z and m have the abovementioned meaning, are reacted with magnesiumin the presence of an inert diluent, such as, for example, diethylether, at temperatures between 0° C. and 50° C.

The benzyl halides of the formula (X) are generally known compounds oforganic chemistry.

Possible diluents in the above process for the preparation of propanolderivatives of the formula (II) are all the inert organic solvents whichare customary for such reactions. Solvents which can preferably be usedare ethers, such as diethyl ether, tetrahydrofuran and dioxane.

The reaction temperatures can be varied within a certain range incarrying out the above process for the preparation of propanolderivatives of the formula (II). The reaction is in general carried outat temperatures between -80° C. and +50° C., preferably between -80° C.and 40° C.

The above process for the preparation of propanol derivatives of theformula (II) is in general carried out under normal pressure. However,it is also possible for the process to be carried out under increased orreduced pressure.

In carrying out the above process for the preparation of propanolderivatives of the formula (II), in general 1 to 1.2 mols oforganometallic compound of the formula (VI) are employed per mol ofcyclopropyl ketone of the formula (VIII) and are advantageously preparedimmediately beforehand and further processed in situ. Working up is bycustomary methods. A procedure is in general followed in which thereaction mixture is first acidified, water is added and the organicphase is then separated off, washed and, after drying, concentrated.

The azoles of the formula (III) required as reaction components forcarrying out process (a) according to the invention are generally knowncompounds of organic chemistry.

Possible acid-binding agents in carrying out process (a) according tothe invention are all the customary inorganic and organic bases. Baseswhich can preferably be used are alkali metal carbonates, such as sodiumcarbonate and potassium carbonate, and furthermore alkali metalhydroxides, such as sodium hydroxide and potassium hydroxide, and inaddition alkali metal alcoholates, such as sodium methylate and ethylateand potassium methylate and ethylate and potassium tert.-butylate, andmoreover lower tertiary alkylamines, cycloalkylamines and aralkylamines,such as, in particular, triethylamine.

Possible diluents in carrying out process (a) according to the inventionare all the customary inert organic solvents. Solvents which canpreferably be used are nitriles, such as acetonitrile, and furthermorearomatic hydrocarbons, such as benzene, toluene and dichlorobenzene, andalso formamides, such as dimethylformamide, as well as strongly polarsolvents, such as dimethyl sulphoxide and hexamethylphosphoric acidtriamide.

The reaction temperatures can be varied within a substantial range incarrying out process (a) according to the invention. The reaction is ingeneral carried out at temperatures between 0° C. and 200° C.,preferably between 60° C. and 150° C.

Process (a) according to the invention, like processes (b), (c) and (d)according to the invention, is in general carried out under normalpressure. However, it is in each case also possible to carry out theprocess under increased or reduced pressure.

In carrying out process (a) according to the invention, in general 1 to4 mols of azole of the formula (III) and 1 to 3 mols of acid-bindingagent are employed per mol of propanol derivative of the formula (II).In some cases, it is advantageous to work under an inert gas atmosphere.Working up is by customary methods. A procedure is in general followedin which the reaction mixture is concentrated by stripping off thediluent, the residue which remains is taken up in an organic solvent oflow water-miscibility and the organic phase is washed and, after drying,concentrated. If appropriate, the product which remains can be subjectedto further purification processes.

Formula (IV) provides a general definition of the oxiranes required asstarting substances in process (b) according to the invention. In thisformula, R, Z and m preferably have those meanings which have alreadybeen mentioned as preferred for these radicals and this index inconnection with the description of the substances of the formula (I)according to the invention.

The oxiranes of the formula (IV) are as yet still unknown. They can beprepared by a process in which propanol derivatives of the formula##STR28## in which

R, Z, Hal and m have the abovementioned meaning, are reacted with basesin the presence of a diluent.

Possible bases in the preparation of oxiranes of the formula (IV) by theabove process are all the inorganic and organic bases which are usuallysuitable for such reactions. All those bases which have already beenmentioned as preferred acid-binding agents in connection with thedescription process (a) according to the invention can preferably beused.

The reaction temperatures can be varied within a certain range in thepreparation of oxiranes by the above process. The reaction is in generalcarried out at temperatures between 0° C. and 100° C., preferablybetween 20° C. and 60° C.

The above process for the preparation of oxiranes of the formula (IV) isin general carried out under normal pressure. However, it is alsopossible for the process to be carried out under increased or reducedpressure.

In carrying out the above process for the preparation of oxiranes of theformula (IV), in general 1 to 3 mols of base are employed per mol ofpropanol derivative of the formula (II). Working up is by customarymethods.

Possible acid-binding agents and diluents in carrying out process (b)according to the invention are all the acid-binding agents and diluentswhich can usually be employed for such reactions. All those acid-bindingagents and diluents which have already been mentioned as preferredacid-binding agents and diluents in connection with the description ofprocess (a) according to the invention can preferably be used.

The reaction temperatures can be varied within a substantial range incarrying out process (b) according to the invention. The reaction is ingeneral carried out at temperatures between 0° C. and 200° C.,preferably between 60° C. and 150° C.

In carrying out process (b) according to the invention, in general 1 to2 mols of azole of the formula (III) and 1 to 2 mols of acid-bindingagent are employed per mol of oxirane of the formula (IV). Working up isby customary methods.

Formula (V) provides a general definition of the azolylmethyl ketonesrequired as starting substances in process (c) according to theinvention. In this formula, R and X preferably have those meanings whichhave already been mentioned as preferred for these radicals inconnection with the description of the substances of the formula (I)according to the invention. The azolylmethyl ketones of the formula (V)are as yet still unknown. They can be prepared by a process in whichcyclopropyl ketones of the formula ##STR29## in which R and Hal" havethe above-mentioned meaning, are reacted with azoles of the formula##STR30## in which X has the above-mentioned meaning, in the presence ofan acid-binding agent and, if appropriate, in the presence of a diluent.

Possible acid-binding agents and diluents in the preparation ofazolylmethyl ketones of the formula (V) by the above process are allacid-binding agents and diluents which are customary for such reactions.All those acid-binding agents which have already been mentioned aspreferred acid-binding agents in connection with the description ofprocess (a) according to the invention can preferably be used. Ketones,such as acetone, and nitriles such as acetonitrile, can preferably beused as diluents.

The reaction temperatures can be varied within a substantial (V) rangein the preparation of azolylmethyl ketones of the formula by the aboveprocess. The reaction is in general carried out at temperatures between0° C. and 120° C., preferably between 20° C. and 100° C.

The above process for the preparation of azolylmethyl ketones of theformula (V) is in general carried out under normal pressure.

In carrying out the above process for the preparation of azolylmethylketones of the formula (V), in general 1 to 4 mols of azole of theformula (III) as well as 1 to 3 mols of acid-binding agent are employedper mol of cyclopropyl ketone of the formula (VIII).

The organometallic compounds of the formula (VI) required as reactioncomponents in process (c) according to the invention have already beenmentioned in connection with the description of the process for thepreparation of the propanol derivatives of the formula (II).

Possible diluents in carrying out process (c) according to the inventionare all customary inert organic solvents. Ethers, such as diethylether,tetrahydrofurane and dioxane, can preferably be used.

The reaction temperatures can be varied within a substantial range incarrying out process (c) according to the invention. The reaction is ingeneral carried out at temperatures between -80° C. and +60° C.,preferably between -70° C. and +50° C.

In carrying out process (c) according to the invention, in general 0.8to 1 mol of an organometallic compound of the formula (VI), whichadvantageously is prepared immediately before and is further reacted insitu, are employed per mol of azolylmethyl ketone of the formula (V).Working up is by customary methods.

The azolylmethylcyclopropyl derivatives of the formula (Ia) required asstarting substances in process (d) according to the invention arecompounds according to the invention. They are converted into thecorresponding alcoholates in a generally known manner by reaction withsuitable strong bases, such as alkali metal amides or hydrides,quaternary ammonium hydroxides or phosphonium hydroxides, in an inertdiluent, such as, for example, dioxane, at room temperature. R³ in thecompounds of the formula (Ib) accordingly preferably represents analkali metal cation, such as a sodium or potassium cation, or representsa quaternary ammonium or phosphonium cation.

Formula (VII) provides a general definition of the halogen compoundsalso required as starting substances in process (d) according to theinvention. In this formula, R⁴ preferably has those meanings which havealready been mentioned as preferred for the substituent R¹ in connectionwith the description of the substances of the formula (I) according tothe invention, with the exception of the meaning of hydrogen. Hal'preferably represents chlorine, bromine or iodine.

The halogen compounds of the formula (VII) are known or can be preparedby methods which are known in principle.

Possible diluents in carrying out process (d) according to the inventionare inert organic solvents. These include, preferably, ethers, such asdiethyl ether or dioxane; aromatic hydrocarbons, such as benzene; inindividual cases also chlorinated hydrocarbons, such as chloroform,methylene chloride or carbon tetrachloride; and hexamethylphosphoricacid triamide.

The reaction temperatures can be varied within a substantial range incarrying out process (d) according to the invention. The reaction is ingeneral carried out between 0° C. and 120° C., preferably between 20° C.and 100° C.

In carrying out process (d) according to the invention, hydroxycompounds of the formula (Ia) are first reacted with strong bases togive the corresponding alcoholates of the formula (Ib). In thesubsequent stage, 1 to 2 mols of halogen compound of the formula (VII)are preferably employed per mol of an alcoholate of the formula (Ib). Toisolate the end products, the reaction mixture is freed from thesolvent, and water and an organic solvent are added to the residue. Theorganic phase is separated off, worked up in the customary manner andpurified.

In a preferred embodiment, a procedure is advantageously followed inwhich a hydroxy compound of the formula (Ia) is used as the startingsubstance, this is converted into the alkali metal alcoholate by meansof an alkali metal hydride or alkali metal amide in a suitable organicsolvent, and the alcoholate is reacted immediately, without beingisolated, with a halogen compound of the formula (VII), the compounds ofthe formula (I) according to the invention being obtained in oneoperation, an alkali metal halide being eliminated.

According to another preferred embodiment, the preparation of thealcoholates and the reaction with a halogen compound of the formula(VII) are advantageously carried out in a two-phase system, such as, forexample, aqueous sodium hydroxide solution or potassium hydroxidesolution/toluene or methylene chloride, with the addition of 0.01-1 molof a phase transfer catalyst, such as, for example, ammonium orphosphonium compounds, the reaction between the alcoholates and thehalides in the organic phase taking place in the organic phase or at thephase boundary.

The azolylmethyl-cyclopropyl derivatives of the formula (I) obtainableby the processes according to the invention can be converted into acidaddition salts or metal salt complexes.

Those acids which have already been mentioned as preferred acids inconnection with the description of the acid addition salts according tothe invention can preferably be used to prepare acid addition salts ofthe compounds of the formula (I).

The acid addition salts of the compounds of the formula (I) can beobtained in a simple manner by customary salt formation methods, forexample by dissolving a compound of the formula (I) in a suitable inertsolvent and adding the acid, for example hydrochloric acid, and can beisolated in a known manner, for example by filtration, and ifappropriate purified by washing with an inert organic solvent.

Those salts of metals which have already been mentioned as preferredmetal salts in connection with the description of the metal saltcomplexes according to the invention can preferably be used to preparemetal salt complexes of the compounds of the formula (I).

The metal salt complexes of the compounds of the formula (I) can beobtained in a simple manner by customary processes, thus, for example,by dissolving the metal salt in alcohol, for example ethanol, and addingthe solution to compounds of the formula (I). The metal salt complexescan be isolated in a known manner, for example by filtration, and ifappropriate purified by recrystallization.

The active compounds according to the invention have a powerfulmicrobicidal action and can be used as fungicides.

Fungicidal agents in plant protection are employed for combatingPlasmodiophoromycetes, Oomycetes, Chytridiomycetes, Zygomycetes,Ascomycetes, Basidiomycetes and Deuteromycetes.

Some causative organisms of fungal and bacterial diseases which comeunder the generic names listed above may be mentioned as examples, butnot by way of limitation: Xanthomonas species, such as Xanthomonasoryzae; Pseudomonas species, such as Pseudomonas lachrymans; Erwiniaspecies, such as Erwinia amylovora; Pythium species, such as Pythiumultimum; Phytophthora species, such as Phytophthora infestans;Pseudoperonospora species, such as Pseudoperonospora humuli orPseudoperonospora cubense; Plasmopara species, such as Plasmoparaviticola; Peronospora species, such as Peronospora pisi or P. brassicae;Erysiphe species, such as Erysiphe graminis; Sphaerotheca species, suchas Sphaerotheca fuliginea; Podosphaera species, such as Podosphaeraleucotricha; Venluria species, such as Venturia inaequalis; Pyrenophoraspecies, such as Pyrenophora teres or P. graminea (conidia form:Drechslera, syn: Helminthosporium); Cochliobolus species, such asCochliobolus sativus (conidia form: Drechslera, syn: Helminthosporium);Uromyces species, such as Uromyces appendiculatus; Puccinia species,such as Puccinia recondita; Tilletia species, such as Tilletia caries;Ustilago species, such as Ustilago nuda or Ustilago avenae; Pelliculariaspecies, such as Pellicularia sasakii; Pyricularia species, such asPyricularia oryzae; Fusarium species, such as Fusarium culmorum;Botrytis species, such as Botrytis cinerea; Septoria species, such asSeptoria nodorum; Leptosphaeria species, such as Leptosphaeria nodorum;Cercospora species, such as Cercospora canescens; Alternaria species,such as Alternaria brassicae, Pseudocercosporella species, such asPseudocercosporella herpotrichoides.

The good toleration, by plants, of the active compounds, at theconcentrations required for combating plant diseases, permits treatmentof above-ground parts of plants, of vegetative propagation stock andseeds, and of the soil.

The active compounds according to the invention are particularlysuitable for combating cereal diseases and rice diseases, such asPseudocercosporella, and for combating Uromyces and Botrytis inpomiculture, viticulture and vegetable growing.

They can be used with particularly good success against Pyricularia onrice and against Leptosphaeria nodorum, Pyrenophora teres and rust andmildew in cereal crops. The substances according to the invention alsoexhibit a good in vitro action.

The active compounds according to the invention furthermore also haveplant growth-regulating properties.

The active compounds according to the invention engage in the metabolismof the plants and can therefore be employed as growth regulators.

Experience to date of the mode of action of plant growth regulators hasshown that an active compound can also exert several different actionson plants. The actions of the compounds depend essentially on the pointin time at which they are used, relative to the stage of development ofthe plant, and on the amounts of active compound applied to the plantsor their environment and the way in which the compounds are applied. Inevery case, growth regulators are intended to influence the crop plantsin the particular manner desired.

Plant growth-regulating compounds can be employed, for example, toinhibit vegetative growth of the plants. Such inhibition of growth is,inter alia, of economic interest in the case of grasses, since it isthereby possible to reduce the frequency of cutting the grass inornamental gardens, parks and sportsgrounds, on verges, at airports orin fruit orchards. The inhibition of growth of herbaceous and woodyplants on verges and in the vicinity of pipelines or overland lines or,quite generally, in areas in which heavy additional growth of plants isundesired, is also of importance.

The use of growth regulators to inhibit the growth in length of cerealsis also important. The danger of bending ("lodging") of the plantsbefore harvesting is thereby reduced or completely eliminated.Furthermore, growth regulators can strengthen the stem of cereals, whichagain counteracts lodging. The use of growth regulators for shorteningand strengthening the stem enables higher amounts of fertilizer to beapplied to increase the yield, without danger of the cereal lodging.

In the case of many crop plants, inhibition of the vegetative growthmakes denser planting possible, so that greater yields per area ofground can be achieved. An advantage of the smaller plants thus producedis also that the crop can be worked and harvested more easily.

Inhibition of the vegetative growth of plants can also lead to increasesin yield, since the nutrients and assimilates benefit blossoming andfruit formation to a greater extent than they benefit the vegetativeparts of plants.

Promotion of vegetative growth can also frequently be achieved withgrowth regulators. This is of great utility if it is the vegetativeparts of the plants which are harvested. Promoting the vegetative growthcan, however, also simultaneously lead to a promotion of generativegrowth, since more assimilates are formed, so that more fruit, or largerfruit, is obtained.

Increases in yield can in some cases be achieved by affecting the plantmetabolism, without noticeable changes in vegetative growth. A change inthe composition of plants, which in turn can lead to a better quality ofthe harvested products, can furthermore be achieved with growthregulators. Thus it is possible, for example, to increase the content ofsugar in sugar beets, sugar cane, pineapples and citrus fruit or toincrease the protein content in soy beans or cereals. Using growthregulators it is also possible, for example, to inhibit the degradationof desired constituents, such as, for example, sugar in sugar beets orsugar cane, before or after harvesting. It is also possible favorably toinfluence the production or the efflux of secondary plant constituents.The stimulation of latex flux in rubber trees may be mentioned as anexample.

Parthenocarpous fruit can be formed under the influence of growthregulators. Furthermore, the gender of the flowers can be influenced.Sterility of the pollen can also be produced, which is of greatimportance in the breeding and preparation of hybrid seed.

Branching of plants can be controlled by using growth regulators. On theone hand, by breaking the apical dominance the development of sideshoots can be promoted, which can be very desirable, especially in thecultivation of ornamental plants, also in connection with growthinhibition. On the other hand, however, it is also possible to inhibitthe growth of side shoots. There is great interest in this action, forexample, in the cultivation of tobacco or in the planting of tomatoes.

The amount of leaf on plants can be controlled, under the influence ofgrowth regulators, so that defoliation of the plants at a desired pointin time is achieved. Such defoliation is of great importance in themechanical harvesting of cotton, but is also of interest forfacilitating harvesting in other crops, such as, for example, inviticulture. Defoliation of the plants can also be carried out to lowerthe transpiration of the plants before they are transplanted.

The shedding of fruit can also be controlled with growth regulators. Onthe one hand, it is possible to prevent premature shedding of fruit.However, on the other hand, shedding of fruit, or even the fall ofblossom, can also be promoted up to a certain degree ("thinning out") inorder to interrupt the alternance. By alternance there is understood thepeculiarity of some species of fruit to produce very different yieldsfrom year to year, for endogenic reasons. Finally, using growthregulators it is possible to reduce the force required to detach thefruit at harvest time so as to permit mechanical harvesting orfacilitate manual harvesting.

Using growth regulators, it is furthermore possible to achieve anacceleration or retardation of ripening of the harvest product, beforeor after harvesting. This is of particular advantage, since it isthereby possible to achieve optimum adaptation to market requirements.Furthermore, growth regulators can in some cases improve the colorationof fruit. In addition, concentrating the ripening within a certainperiod of time is also achievable with the aid of growth regulators.This provides the preconditions for being able to carry out completemechanical or manual harvesting in only a single pass, for example inthe case of tobacco, tomatoes or coffee.

Using growth regulators, it is furthermore possible to influence thelatent period of seeds or buds of plants, so that the plants, such as,for example, pineapple or ornamental plants in nurseries, germinate,shoot or blossom at a time at which they normally show no readiness todo so. Retarding the shooting of buds or the germination of seeds withthe aid of growth regulators can be desirable in regions where frost isa hazard, in order to avoid damage by late frosts.

Finally, the resistance of plants to frost, drought or a high saltcontent in the soil can be induced with growth regulators. Cultivationof plants in regions which are usually unsuitable for this purposethereby becomes possible.

The active compounds can be converted to the customary formulations,such as solutions, emulsions, suspensions, powders, foams, pastes,granules, aerosols, very fine capsules in polymeric substances and incoating compositions for seed, and ULV formulations.

These formulations are produced in known manner, for example by mixingthe active compounds with extenders, that is, liquid solvents, liquefiedgases under pressure, and/or solid carriers, optionally with the use ofsurface-active agents, that is, emulsifying agents and/or dispersingagents and/or foam-forming agents. In the case of the use of water as anextender, organic solvents can, for example, also be used as auxiliarysolvents. As liquid solvents, there are suitable in the main: aromatics,such as xylene, toluene or alkyl naphthalenes, chlorinated aromatics orchlorinated aliphatic hydrocarbons, such as chlorobenzenes,chloroethylenes or methylene chloride, aliphatic hydrocarbons, such ascyclohexane or paraffins, for example mineral oil fractions, alcohols,such as butanol or glycol as well as their ethers and esters, ketones,such as acetone, methyl ethyl ketone, methyl isobutyl ketone orcyclohexanone, strongly polar solvents, such as dimethylformamide anddimethylsulphoxide, as well as water; by liquefied gaseous extenders orcarriers are meant liquids which are gaseous at normal temperature andunder normal pressure, for example aerosol propellants, such ashalogenated hydrocarbons as well as butane, propane, nitrogen and carbondioxide; as solid carriers there are suitable: for example groundnatural minerals, such as kaolins, clays, talc, chalk, quartz,attapulgite, montmorillonite or diatomaceous earth, and ground syntheticminerals, such as highly dispersed silicic acid, alumina and silicates;as solid carriers for granules there are suitable: for example crushedand fractionated natural rocks such as calcite, marble, pumice,sepiolite and dolomite, as well as synthetic granules of inorganic andorganic meals, and granules of organic material such as sawdust, coconutshells, corn cobs and tobacco stalks; as emulsifying and/or foam-formingagents there are suitable: for example non-ionic and anionicemulsifiers, such as polyoxyethylene-fatty acid esters,polyoxyethylene-fatty alcohol ethers, for example alkylaryl polyglycolethers, alkyl sulphonates, alkyl sulphates, aryl sulphonates as well asalbumin hydrolysis products; as dispersing agents there are suitable:for example ligninsulphite waste liquors and methylcellulose.

Adhesives such as carboxymethylcellulose and natural and syntheticpolymers in the form of powders, granules or latices, such as gumarabic, polyvinyl alcohol and polyvinyl acetate, as well as naturalphospholipids, such as cephalins and lecithins, and syntheticphospholipids, can be used in the formulations. Other additives can bemineral and vegetable oils.

It is possible to use colorants such as inorganic pigments, for exampleiron oxide, titanium oxide and Prussian Blue, and organic dyestuffs,such as alizarin dyestuffs, azo dyestuffs and metal phthalocyaninedyestuffs, and trace nutrients such as salts of iron, manganese, boron,copper, cobalt, molybdenum and zinc.

The formulations in general contain between 0.1 and 95 percent by weightof active compound, preferably between 0.5 and 90%.

The active compounds according to the invention can be present in theformulations as a mixture with other known active compounds, such asfungicides, insecticides, acaricides and herbicides, and in mixtureswith fertilizers and other growth regulators.

The active compounds can be used as such or in the form of theirformulations or the use forms prepared therefrom, such as ready-to-usesolutions, emulsifiable concentrates, emulsions, foams, suspensions,wettable powders, pastes, soluble powders, dusts and granules. They areused in the customary manner, for example by watering, spraying,atomizing, scattering, dusting, foaming, brushing on and the like. It isfurthermore possible to apply the active compounds by the ultra-lowvolume method or to inject the active compound formulation or the activecompound itself into the soil. The seed of the plants can also betreated.

When the substances according to the invention are used as fungicides,the amount applied can be varied within a substantial range, dependingon the type of application. In the treatment of parts of plants, theactive compound concentrations in the use forms are thus in generalbetween 1 and 0.0001% by weight, preferably between 0.5 and 0.001%. Inthe treatment of seed, amounts of active compound of 0.001 to 50 g perkilogram of seed, preferably 0.01 to 10 g, are generally required. Forthe treatment of soil, active compound concentrations of 0.00001 to 0.1%by weight, preferably 0.0001 to 0.02%, are required at the place ofaction.

When the compounds according to the invention are used as plantgrowth-regulators, the amounts applied can be varied within asubstantial range. In general, 0.01 to 50 kg, preferably 0.05 to 10 kgof active compound are used per hectare of soil surface.

When the substances according to the invention are used as plant growthregulators, the rule is that the application is carried out in apreferred period of time, the exact definition of which depends on theclimatic and vegetative circumstances.

The preparation and the use of the active compounds according to theinvention can be seen from the following examples.

PREPARATION EXAMPLES EXAMPLE 1 ##STR31##

65 g (0.94 mol) of 1,2,4-triazole and 71 g (0.63 mol) of potassiumtert.-butylate are taken in 160 ml of absolute dimethylformamide under anitrogen atmosphere and are heated to 80° C. A solution of 70.6 g (0.26mol) of 1-chloro-2-(1-chlorocyclopropyl)-3-(4-fluorophenyl)-propan-2-olin 90 ml of absolute dimethylformamide is added dropwise at thistemperature, with stirring. The mixture is subsequently stirred at 100°C. for 6 hours and is then concentrated by stripping off the diluentunder reduced pressure. The residue is taken up in ethyl acetate, themixture is washed with water and, after drying over sodium sulphate, thesolvent is stripped off under reduced pressure. The product whichremains is chromatographed over a silica gel column with chloroform asthe mobile phase. 28.2 g (39% of theory) of1-(4-fluorophenyl)-2-(1-chloro-cyclopropyl)-3-(1,2,4-triazol-1-yl)-propan-2-olare obtained in this manner in the form of a solid substance of meltingpoint 111° C.

Preparation of precursors: ##STR32##

A solution of 65.7 g (0.35 mol) of 4-fluorobenzyl bromide in 430 ml ofabsolute diethyl ether is added dropwise to a mixture of 9.3 g (0.38mol) of magnesium filings in 185 ml of diethyl ether at roomtemperature. The mixture is heated under reflux for 30 minutes, and thesolution formed is then added dropwise to a solution of 47.8 g (0.32mol) of 1-chloro-1-chloroacetyl-cyclopropane in 300 ml of absolutediethyl ether at -78° C., with stirring. The reaction mixture is stirredat -78° C. for 4 hours. Thereafter, it is allowed to warm slowly to 0°C., and a solution of 31 ml of acetic acid in 300 ml of diethyl ether isthen added dropwise. The reaction mixture formed is poured onto 1,200 mlof water. The organic phase is separated off, washed with aqueous sodiumbisulphite solution and with water, dried over sodium sulphate andconcentrated under reduced pressure. 70.6 g (86% of theory) of1-chloro-2-(1-chloro-cyclopropyl)-3-(4-fluoro-phenyl)-propan-2-ol areobtained in the form of an oily product.

¹ H--NMR (200 MHz, CDCl₃): δ=0.6-1.2 (m, 4H); 3.05 (d, 1H); 3.15 (d,1H);3.75 (d, 1H); 4.03 (d, 1H); 7.0 (t, 2H); 7.22-7.37 (m, 2H). ##STR33##

40.5 ml (0.5 mol) of sulphuryl chloride are slowly added dropwise to asolution of 54 g (0.46 mol) of 1-acetyl-1-chloro-cyclopropane in 250 mlof methylene chloride at room temperature with stirring. The mixture isstirred first at room temperature for 14 hours and then at 30° C. for 30minutes. The reaction mixture is then washed with saturated aqueoussodium bicarbonate solution and with water in succession. Thereafter,the organic phase is dried over sodium sulphate and concentrated underreduced pressure. 51.5 g (74% of theory) of1-chloro-1-chloroacetyl-cyclopropane are obtained in this manner in theform of an oily substance.

¹ H--NMR (60 MHz, CDCl₃): δ=1.2-1.9 (m, 4H); 4.8 (s, 8H)

The compound of the formula ##STR34## can also be prepared by process(c) according to the invention by reacting(1,2,4-triazol-1-yl-methyl)-(1-chloro-cycloprop-1-yl)-ketone with4-fluorobenzyl magnesium bromide in the presence of diethyl ether.

Preparation of the starting substance of the formula ##STR35## Asolution of 60 g of 1-acetyl-1-chloro-cyclopropane in 50 ml of acetoneis added dropwise to a solution of 50 g of potassium carbonate and 35 gof 1,2,4-triazole in 200 ml of acetone, while stirring at roomtemperature and under nitrogen atmosphere. The mixture is heated for 8hours under reflux, then it is concentrated by stripping off the diluentunder reduced pressure, the residue is taken up in a mixture of ethylacetate and toluene, the mixture is washed with water, dried over sodiumsulphate and concentrated under reduced pressure 38 9 g of(1,2,4-triazol-1-yl-methyl)-(1-chloro-cycloprop-1-yl)-ketone areobtained in this manner in the form of a solid substance of meltingpoint 79° C.

¹ H--NMR (200 MHz, CDCl₃): δ=1.50 (m, 2H), 1.78 (m, 2H), 5.62 (s, 2H),7.98 (s, 1H), 8.14 (s, 1M).

The azolylmethyl-cyclopropyl derivatives of the formula (I) which areshown in the following table are also prepared by the methods which arementioned in Example 1 and in the description.

                  TABLE                                                           ______________________________________                                         ##STR36##                     (I)                                            Example                              Melting point                            No.       Z.sub.m R.sup.1 X    R     (°C.)                             ______________________________________                                         2        2-F     H       N    Cl    103                                       3        2,4-F.sub.2                                                                           H       N    Cl    117                                       4        2-Cl    H       N    Cl    108                                       5        3,4-Cl.sub.2                                                                          H       N    Cl    80-92                                     6        --      H       N    Cl    81                                        7        4-Cl    H       N    Cl    97                                        8        2,4-Cl.sub.2                                                                          H       N    Cl    159                                       9        4-CH.sub.3                                                                            H       N    Cl    132                                      10        3,4-F.sub.2                                                                           H       N    Cl    98                                       11        4-F     H       CH   Cl    171                                      ______________________________________                                    

The compounds of the formulae shown below were employed as comparisonsubstances in the use examples which follows: ##STR37##

EXAMPLE A

Botrytis test (bean)/protective

Solvent: 4.7 parts by weight of acetone

Emulsifier: 0.3 parts by weight of alkylaryl polyglycol ether.

To produce a suitable preparation of active compound, 1 part by weightof active compound is mixed with the stated amounts of solvent andemulsifier, and the concentrate is diluted with water to the desiredconcentration.

To test for protective activity, young plants are sprayed with thepreparation of active compound until dripping wet. After the spraycoating has dried on, 2 small pieces of agar covered with Botrytiscinerea are placed on each leaf. The inoculated plants are placed in adarkened humid chamber at 20° C. 3 days after the inoculation, the sizeof the infected spots on the leaves is evaluated.

In this test, the compound (I-1) according to the invention has aconsiderably better activity than the comparison substances (A) and (C).

EXAMPLE B

Uromyces test (dwarf bean)/protective

Solvent: 4.7 parts by weight of acetone

Emulsifier: 0.3 parts by weight of alkylaryl polyglycol ether.

To produce a suitable preparation of active compound, 1 part by weightof active compound is mixed with the stated amounts of solvent andemulsifier, and the concentrate is diluted with water to the desiredconcentration.

To test for protective activity, young plants are sprayed with thepreparation of active compound until dripping wet. After the spraycoating has dried on, the plants are inoculated with an aqueousuredospore suspension of the bean rust causative organism (Uromycesappendiculatus) and remain in a dark humidity chamber at 20° to 22° C.and 100% relative atmospheric humidity for 1 day.

The plants are then placed in a greenhouse under intensive illuminationat 20° to 22° C. and a relative atmospheric humidity of 70 to 80% for 9days.

Evaluation is carried out 10 days after the inoculation.

In this test, the compound (I-1) according to the invention has aconsiderably better activity than the comparison substances (A), (B) and(C).

EXAMPLE C

Venturia test (apple)/protective

Solvent: 4.7 parts by weight of acetone

Emulsifier: 0.3 parts by weight of alkylaryl polyglycol ether.

To produce a suitable preparation of active compound, 1 part by weightof active compound is mixed with the stated amounts of solvent andemulsifier, and the concentrate is diluted with water to the desiredconcentration.

To test for protective activity, young plants are sprayed with thepreparation of active compound until dripping wet. After the spraycoating has dried on, the plants are inoculated with an aqueous conidiasuspension of the apple scab causative organism (Venturia inaequalis)and then remain in an incubation cabin at 20° C. and 100% relativeatmospheric humidity for 1 day.

The plants are then placed in a greenhouse at 20° C. and a relativeatmospheric humidity of about 70%.

Evaluation is carried out 12 days after the inoculation.

In this test, the compound (I-1) according to the invention has aconsiderably better action than the comparison substances (A) and (C).

EXAMPLE D

Pseudocercosporella herpotrichoides test (wheat)/protective

Solvent: 100 parts by weight of dimethylformamide

Emulsifier: 0.25 parts by weight of alkylaryl polyglycol ether.

To produce a suitable preparation of active compound, 1 part by weightof active compound is mixed with the stated amounts of solvent andemulsifier, and the concentrate is diluted with water to the desiredconcentration.

To test for protective activity, young plants are sprayed with thepreparation of active compound until dew moist. After the spray coatinghas dried on, the plants are inoculated at the stem base with spores ofPseudocercosporella herpotrichoides.

The plants are placed in a greenhouse at a temperature of about 10° C.and a relative atmospheric humidity of about 80%.

Evaluation is carried out 21 days after the inoculation.

In this test, the compound (I-1) according to the invention has a verygood activity.

EXAMPLE E

Erysiphe test (barley)/seed treatment

The active compounds are used as dry dressings. These are prepared byextending the particular active compound with a ground mineral to give afinely pulverulent mixture, which ensures uniform distribution on theseed surface.

To apply the dressing, the seed is shaken with the dressing in a closedglass flask for 3 minutes.

3 batches of 12 grains of the barley are sown 2 cm deep in standardsoil. 7 days after sowing, when the young plants have unfolded theirfirst leaf, they are dusted with spores of Erysiphe graminis f. sp.hordei.

The plants are placed in a greenhouse at a temperature of about 20° C.and a relative atmospheric humidity of about 80% in order to promote thedevelopment of powdery mildew pustules.

Evaluation is carried out 7 days after the inoculation.

In this test, the compound (I-1) according to the invention shows aconsiderably better activity than the comparison substance (A).

EXAMPLE F

Leptosphaeria nodorum-test (wheat)/protective

Solvent: 100 parts by weight of dimethylformamide

Emulsifier: 0.25 parts by weight of alkylaryl polyglycol ether.

To produce a suitable preparation of active compound, 1 part by weightof active compound is mixed with the stated amounts of solvent andemulsifier, and the concentrate is diluted with water to the desiredconcentration.

To test for protective activity, young plants are sprayed with thepreparation of active compound until dew-moist. After the spray coatinghas dried on, the plants are sprayed with a conidium suspension ofLeptosphaeria nodorum. The plants remain in an incubation cabin at 20°C. and 100% relative atmospheric humidity for 48 hours.

The plants are placed in a greenhouse at a temperature of about 15° C.and a relative atmospheric humidity of about 80%.

Evaluation is carried out 10 days after the inoculation.

In this test, the compound (I-1) according to the invention shows aconsiderably better activity than the comparison substances (D).

EXAMPLE G

Pyrenophora teres test (barley)/protective

Solvent: 100 parts by weight of dimethylformamide

Emulsifier: 0.25 parts by weight of alkylaryl polyglycol ether.

To produce a suitable preparation of active compound, 1 part by weightof active compound is mixed with the stated amounts of solvent andemulsifier, and the concentrate is diluted with water to the desiredconcentration.

To test for protective activity, young plants are sprayed with thepreparation of active compound until dew-moist. After the spray coatinghas dried off, the plants are sprayed with a conidia suspension ofPyrenophora teres. The plants then remain in an incubation cabin at 20°C. and 100% relative atmospheric humidity for 48 hours.

The plants are placed in a greenhouse at a temperature of about 20° C.and a relative atmospheric humidity of about 80%.

Evaluation is carried out 7 days after the inoculation.

In this test, the compound (I-1) according to the invention shows aconsiderably better activity than the comparison substance (D).

It is understood that the specification and examples are illustrativebut not limitative of the present invention and that other embodimentswithin the spirit and scope of the invention will suggest themselves tothose skilled in the art.

We claim:
 1. A propanol derivative of the formula ##STR38## in which Rrepresents halogen, alkyl with 1 to 6 carbon atoms or phenyl optionallysubstituted by halogen, halogenoalkyl with 1 or 2 carbon atoms and 1 to5 halogen atoms, alkyl with 1 to 4 carbon atoms and/or alkoxy with 1 to4 carbon atoms and/or alkoxy with 1 to 4 carbon atoms, or represents thegrouping -Y-R²,wherein Y represents oxygen, sulphur, SO or SO₂ and R²represents phenyl which is optionally substituted by halogen,halogenoalkyl with 1 or 2 carbon atoms and 1 to 5 halogen atoms, alkylwith 1 to 4 carbon atoms and/or alkoxy with 1 to 4 carbon atoms, Halrepresents chlorine, bromine or iodine, Z represents halogen, alkyl with1 to 4 carbon atoms, alkoxy with 1 to 4 carbon atoms, alkylthio with 1to 4 carbon atoms, halogenoalkyl with 1 or 2 carbon atoms and 1 to 5halogen atoms, halogenoalkoxy with 1 or 2 carbon atoms and 1 to 5halogen atoms, halogenoalkylthio with 1 to 2 carbon atoms and 1 to 5halogen atoms or phenyl which is optionally substituted by alkyl with 1or 2 carbon atoms and/or halogen, or represents phenoxy which isoptionally substituted by alkyl with 1 or 2 carbon atoms and/or halogenand m represents the number 0, 1, 2 or
 3. 2. A compound according toclaim 1, in whichR represents fluorine, chlorine, bromine or alkyl with1 to 6 carbon atoms, or represents phenyl which is optionallysubstituted by halogen, halogenoalkyl with 1 or 2 carbon atoms and 1 to5 halogen atoms, alkyl with 1 to 4 carbon atoms and/or alkoxy with 1 to4 carbon atoms, or represents the grouping -Y-R²,wherein Y representsoxygen, sulphur, SO or SO₂, R² represents phenyl which is optionallysubstituted by halogen, halogenoalkyl with 1 or 2 carbon atoms and 1 to5 halogen atoms, alkyl with 1 to 4 carbon atoms and/or alkoxy with 1 to4 carbon atoms, Z represents halogen, alkyl with 1 to 4 carbon atoms,alkoxy with 1 to 4 carbon atoms, alkylthio with 1 to 4 carbon atoms,halogenoalkyl with 1 or 2 carbon atoms and 1 to 5 halogen atoms,halogenoalkoxy with 1 or 2 carbon atoms and 1 to 5 halogen atoms,halogenoalkylthio with 1 or 2 carbon atoms and 1 to 5 halogen atoms orphenyl which is optionally substituted by alkyl with 1 or 2 carbon atomsand/or halogen, or represents phenoxy which is optionally substituted byalkyl with 1 or 2 carbon atoms and/or halogen and m represents thenumber 0, 1, 2 or
 3. 3. A compound according to claim 2, in whichRrepresents fluorine, chlorine, bromine, methyl ethyl or phenyl which isoptionally substituted by one to three identical or differentsubstituents from the group comprising fluorine, chlorine, bromine,trifluoromethyl, ethyl, ethyl, methoxy and/or ethoxy, or represents thegrouping -Y-R², and Z represents fluorine, chlorine, bromine, methyl,ethyl, isopropyl, tert.-butyl, methoxy, methylthio, trifluoromethyl,trifluoromethoxy, trifluoromethylthio or phenyl which is optionallysubstituted by fluorine, chlorine and/or methyl, or represents phenoxywhich is optionally substituted by fluorine, chlorine and/or methyl. 4.A compound according to claim 3, in whichR represents chlorine, Zrepresents halogen, and m represents the number 1 or 2.